Mass spectrometry is undeniably one of the most important and commonly used analytical tools to detect, identify and quantitate molecules. Given its sensitivity and selectivity, mass spectrometry is particularly important in life science applications. Among the different methods developed up to date for the introduction of the analytes into the mass spectrometer, electrospray ionization (ESI) is acknowledged as the ultimate approach for ionization of molecules in solution phase. Despite its multiple advantages, extensive, expensive and elaborate sample-preparation/separation steps are commonly required to analyze complex sample (e.g. blood, saliva, or urine) by ESI. In order to increase the speed of analysis and minimize the sample treatment, ambient ionization methods were introduced. In essence, the main goal of ambient ionization is to ionize analytes under an ambient environment from condensed-phase samples with minimal or nil sample preparation and/or separation. Thus, these modern techniques offer an attractive solution for real-time and on-site analysis of complex samples. Among this family of techniques, desorption electrospray ionization (DESI) and direct analysis in real time (DART) have become the most established. In essence, these techniques “wipe-off” analytes from the samples by exposing their surfaces to an ionizing medium which is essentially a gas or an aerosol. Although these techniques have provided significant advances in environmental, forensic, clinical and food applications, their operation generally requires sophisticated and costly equipment (e.g. source of high pressure gas for pneumatic assistance, pumping means to provide a continuous flow of a solvent, and feedback-controlled electronics for sample positioning). Other techniques combining sampling and ionization are also being used for these types of analyses, including laser ablation electrospray ionization (LAESI), liquid extraction surface analysis (LESA) and paper spray ionization. Individually these techniques have some advantages, however none of them combine all of these functions in a single apparatus: (i) collecting a sample, (ii) enriching it relative to its initial concentration in the sample, (iii) preparing said sample for analysis, and (iv) ionizing it for analysis by a mass spectrometer. Consequently, an analytical chemistry technique capable of combining sampling, sample preparation, analyte enrichment, and ionization in a single apparatus with simple instrumentation requirements is an unmet need for chemical analysis.